CN115667464A - 用于净化热解塑料废料的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims description 6
- 238000004140 cleaning Methods 0.000 title abstract 2
- 238000000197 pyrolysis Methods 0.000 title description 9
- 229920003023 plastic Polymers 0.000 title description 6
- 239000004033 plastic Substances 0.000 title description 6
- 239000013502 plastic waste Substances 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
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- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005202 decontamination Methods 0.000 claims description 2
- 230000003588 decontaminative effect Effects 0.000 claims description 2
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- 238000004230 steam cracking Methods 0.000 abstract description 3
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- 150000002430 hydrocarbons Chemical class 0.000 description 16
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- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
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- 238000004458 analytical method Methods 0.000 description 3
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- 239000000460 chlorine Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- 239000010817 post-consumer waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及用于净化热解塑料废料的方法,该方法包括以下步骤:提供热解塑料废料,其中,所述热解塑料废料在20℃和1atm下为液体或蜡;将热解塑料废料与活性炭接触,产生预处理塑料废料;以及使用氢气和金属基催化剂对预处理塑料废料进行氢化,产生适合于蒸汽裂化的氢化塑料废料。
Description
技术领域
本发明涉及用于净化热解塑料废料的方法,特别是用于净化在20℃和1atm下为液体或蜡的热解塑料废料的方法。
背景技术
目前塑料废料的热解通常在350-600℃的温度范围内进行,停留时间足以将长聚合物链分解成更小的片段。对于以聚烯烃和/或聚氯乙烯为基础或由其产生的塑料废料,产生的产品是不同烃片段的混合物。根据工艺条件的不同,所述塑料废料可转化为液体产品,作为蒸汽裂化器的原料。
这些工艺在现有技术中基本已知。例如,美国专利申请US 2016/0264874 A1公开了一种将废塑料转化为高价值产品的工艺。该工艺允许使用单个加氢处理反应器进行操作,可同时对烃流组分进行加氢、脱氯和加氢裂化,以满足蒸汽裂化器要求的规格,并可选择在抛光区进一步对处理过的烃流进行脱氯。
在PCT申请WO 2018/025103 A1中,进一步描述了一种处理烃原料以满足某些蒸汽裂化器原料要求的方法,这些烃原料来自废塑料。
PCT申请WO 2018/055555 A1公开了一种用于处理塑料废料的进一步热解工艺。所公开的工艺包括以下步骤:将塑料废料转化为烃液和第一C1-4气体;将烃液与加氢处理单元中的第一加氢处理催化剂接触,产生第二C1-4气体和第一烃产品,其包括C5+液态烃类;将第一烃产品引入第一分离单元,以产生含有C5-8烃类的处理过的烃流和含有C9+烃类的第一重流;在加氢脱烷基单元中,使第一重流与第二加氢处理催化剂接触,以产生第二烃产品,其包括C5+液态烃类和第三C1-4气体;将第二烃产品输送到第一分离单元;将处理过的烃流送入蒸汽裂化器以产生蒸汽裂化器产品;将蒸汽裂化器产品分离为烯烃气、饱和烃气、芳烃和第二重流;将第二重流输送到加氢处理单元。
虽然处理塑料废料的热解方法在现有技术中是众所周知的,但该方法仍需要改进。
因此,本发明的目的是提供用于净化热解塑料废料的改进方法。
发明内容
这个目的被根据权利要求1的方法解决。从属的权利要求显示了本发明的有利实施方式。
令人惊讶的是,研究发现,使用活性炭对热解塑料废料(pyrolyzed plasticwaste)进行预处理,然后对预处理塑料废料(pretreated plastic waste)进行氢化,带来了热解塑料废料中存在的所有杂质更大程度的降低。在随后的氢化步骤中,可以观察到的另一个优势是去芳构化,这是特别有益的,因为它将预处理塑料废料中存在的芳香化合物转化为环烷烃类,与芳香化合物不同的是,环烷烃类在蒸汽裂化过程中可以转化为烯烃类。
根据本发明,因此,用于净化热解塑料废料的方法包括以下步骤:
a)提供热解塑料废料,其中,所述热解塑料废料在20℃和1atm下为液体或蜡;
b)将所述热解塑料废料与活性炭接触,产生预处理塑料废料;和
c)使用氢气和金属基催化剂对所述预处理塑料废料进行氢化,产生氢化塑料废料。
本发明方法能够去除不必要的杂质,如氧、氮、硫和氯,同时增加了液体的稳定性,因为液体中存在的二烯烃类和烯烃类已经饱和。活性炭对热解塑料废料的预处理为步骤c)中的杂质去除额外提供了增加的趋势。氢化塑料废料优选适合于蒸汽裂化。因此,从经济和环境的角度来看,该方法都是有利的。
在优选实施方式中,塑料废料包括含有聚烯烃、聚氯乙烯、聚苯乙烯或其混合物的废料,进一步优选由含有聚烯烃、聚氯乙烯、聚苯乙烯或其混合物的废料组成。
本文所使用的术语“塑料废料”优选指消费后废塑料,如聚烯烃、聚氯乙烯、聚苯乙烯或其混合物废料。典型的聚烯烃消费后废塑料可包括聚乙烯,即低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)和聚丙烯(PP)。
根据本发明,所述热解塑料废料在20℃和1atm下为液体或蜡。例如,液体是油。蜡被定义为在1atm下40℃以上熔化的物质。这种热解塑料废料包括前消费后废塑料的长聚合物链的不同片段。
热解塑料废料优选可通过热解工艺获得,其中,消费后塑料废料,如聚烯烃、聚氯乙烯或其混合物被送入热解反应器,如固定床、流化床、锥形喷动床、运输床反应器、搅拌槽反应器和/或窑型反应器,并且随后在适当催化剂的存在下,在350-600℃的温度范围内被热解。上述工艺条件可以进行选择,以使所述塑料废料产生液体产品。
本文中使用的术语“活性炭”是指多孔碳材料,它具有高度发达的多孔结构和大的比表面积,优选为颗粒或小球的形式。活性炭的比表面积(BET)优选为100-1000m2/g,进一步优选为300-700m2/g,进一步优选为500-600m2/g,进一步优选为545-555m2/g,比表面积(BET)进一步优选为550m2/g。
步骤b)优选在第一容器中进行。第一容器可以是任何种类的适合于使热解塑料废料与活性炭接触的容器,例如钢容器。优选地,第一容器是包含搅拌器或混合器的容器,或第一容器是包含活性炭床的容器。搅拌器或混合器用于搅拌或混合容器内存在的塑料废料和活性炭。
将步骤b)中获得的预处理塑料废料优选地从第一容器转移到用于氢化步骤c)的第二容器中。例如,可以通过连接第一容器和第二容器的管道进行转移。
在优选实施方式中,本发明方法的步骤b)通过混合塑料废料和活性炭进行,更优选地,通过搅拌塑料废料和活性炭进行,或者本发明方法的步骤b)通过使热解塑料废料流动经过活性炭床进行。
优选地,步骤b)在5℃至100℃的温度范围内进行,更优选在10℃至50℃的范围内,更优选在15℃至30℃的范围内,最优选地,在室温下进行和/或步骤b)优选在常压下进行。
优选地,步骤b)在相对于热解塑料废料量为0.1-110 1/h的重量时空速度(WHSV)下进行,更优选为0.1-50 1/h,更优选为0.1-20 1/h,更优选为0.1-5 1/h,更优选为0.2-31/h,更优选为0.25-1.0 1/h,甚至更优选为0.3 1/h。
通常,b)步骤中的接触是在实验室规模的反应器中进行的,与工业规模的反应器相比,其WHSV更高,即高达110 1/h。
步骤b)的WHSV计算如下:
优选地,在步骤c)之前进行步骤b)。
优选地,在不同于步骤c)的条件下进行步骤b),这些条件是温度和/或压力。优选地,步骤b)在进行时的温度要低于步骤c)进行时的温度和/或步骤b)在进行时的压力要低于步骤c)进行时的压力。
优选地,步骤c)在第二容器中进行,第二容器优选为反应器。第二容器,优选的反应器,可以是任何类型的容器或反应器,只要其分别适用于使用氢气和金属基催化剂对预处理塑料废料进行氢化。反应器优选为实验室规模的反应器,如高压釜反应器或工业规模的反应器。
优选地,步骤b)和步骤c)不在同一容器中进行。换句话说,步骤b)和步骤c)优选为分开的步骤,特别是在空间上分开的步骤,优选步骤b)在第一容器中进行,步骤c)在第二容器中进行。
优选地,第一容器不同于第二容器。
在金属基催化剂的存在下进行预处理塑料废料的氢化。催化剂可以是能够使预处理塑料废料液中的烯烃、二烯烃和芳族化合物氢化(即饱和)的任何催化剂。因此,合适的金属基催化剂可以包含至少一种金属和载体。载体还可以包含从由二氧化硅、碳和/或金属氧化物及其混合物组成的列表中选择的化合物,优选由从由二氧化硅、碳和/或金属氧化物及其混合物组成的列表中选择的化合物组成。
优选地,用于金属基催化剂的载体的比表面积(BET)为100-1000m2/g,更优选为200-300m2/g,更优选为220-280m2/g,更优选为250m2/g。BET是根据ASTM D3663测量的。
本文使用的术语“金属氧化物”是指从第4-13组金属中选择的一种金属的氧化物。
在优选实施方式中,载体包含第13组金属氧化物,更优选由第13组金属氧化物组成,最优选包括氧化铝或由氧化铝组成,优选的形式为Al2O3。
载体的平均粒径可以在宽的范围内变化。优选的范围是1-5mm,更优选为2-4mm,更优选为2.5-3.5mm,更优选为3mm。
载体的平均孔隙体积可以在宽的范围内变化。优选的范围是0.50-1.5ml/g,更优选为0.80-1.1mL/g,更优选为1.00mL/g。
金属基催化剂的金属可以包括(优选是)从第6组金属和/或第9-11组金属列表中选择的金属,更优选由从第6组金属和/或第10组金属列表中选择的金属组成。这些金属包括钴(Co)、钼(Mo)、铑(Rh)、铱(Ir)、镍(Ni)、钯(Pd)、铂(Pt)、铜(Co)、银(Ag)和/或金(Au)。
在优选实施方式中,金属基催化剂的金属包括钯,优选由钯组成。
在进一步的优选实施方式中,金属基催化剂的金属可包括选自过渡金属组中至少两种金属的组合,如镍和钴(Ni-Co)或钴和钼(Co-Mo)。
金属基催化剂中的金属含量不应超过10wt.%,优选不超过7.5wt.%,更优选不超过6wt.%。如果金属基催化剂中的金属含量过高,氢化反应可能会受到影响。另一方面,金属基催化剂中的金属含量不宜过低。因此,金属基催化剂中的金属含量至少为0.1wt.%,优选为至少0.5wt.%,更优选为至少1wt.%,优选为含量在3.3-3.7wt.%的范围内,更优选为3.5wt.%,还更优选为在3.8-4.2wt.%的范围内,例如4wt.%。
在优选实施方式中,金属基催化剂以4.8-5.2wt.%的量包括金属,最优选为5wt.%,其中,金属优选包括钯,优选由钯组成。
例如,可以通过使用挥发性溶剂由金属组分制备溶液,然后将金属溶液与相应的载体接触并蒸发溶剂来制备金属基催化剂。
为了增强用于预处理塑料废料氢化的金属基催化剂的活性,所述催化剂优选被预活化,更优选为在氢气的存在下被预活化。金属基催化剂可通过使催化剂与包含氢气的活化流相接触而被活化。氢气可以以压力为10-50bar(优选为20-40bar,更优选为25-35bar,最优选为28-32bar,例如30bar)的气体提供。
金属基催化剂被预活化的合适温度至多350℃,优选为至多300℃,更优选为至多275℃。在一个实施方式中,选择温度为150-350℃,优选为200-300℃,更优选为225-275℃。在优选实施方式中,金属基催化剂在245-255℃(最优选为250℃)的温度下被预活化。
金属基催化剂被预活化的时间周期为0.5-4.0h,优选为1.0-3.5h,更优选为2.0-3.0h,最优选为2.5h。
可供选择地,金属基催化剂可以通过以下被硫化:以严格控制的温度计划,在足够活化金属基催化剂的特定时间周期内,使催化剂与包含一种或多种硫化物和氢气的气流接触。
在优选实施方式中,用于进行预处理塑料废料的氢化步骤c)的氢气以压力至多100bar(优选为至多50bar,更优选为至多40bar,以及更优选为至多35bar)的气体提供。在一个实施方式中,氢气以压力为10-50bar(优选为20-40bar,更优选为25-35bar)的气体提供。在最优选的实施方式中,氢气以30bar的压力提供。
根据步骤c)进行氢化的温度对化学反应动力学有很大影响。因此,温度可至少为200℃,优选至少为250℃,更优选至少为280℃。另一方面,温度不应超过400℃,优选为350℃,更优选为320℃。
在最优选的实施方式中,根据步骤c)进行氢化的温度在290-310℃的范围内,例如300℃。
优选地,在步骤c)中,氢化在相对于预处理塑料废料量为0.1-50.0 1/h的重量时空速度(WHSV)下进行,更优选为0.1-5.0 1/h,优选为0.2-3.01/h,更优选为0.3-2.0 1/h,甚至更优选为0.8-1.2 1/h。
通常,步骤c)中的氢化是在实验室规模的反应器中进行的,与工业规模的反应器相比,其WHSV更高,即高达50 1/h。
步骤c)的WHSV计算如下:
具体实施方式
实施例
采用GC-MS(气相色谱-质谱)和GC-AED(气相色谱-原子发射检测器)对热解塑料废料进行分析。
GC-MS分析使用Agilent GC 6890进行,具有MSD 5975B inert XL。GC柱是AgilentDB1(60m×0.25mm i.d.,膜厚1.0μm)。柱温在40℃下保持3min,然后升至320℃(5℃/min),保持10min。注射器的温度保持在350℃,分流比30:1。液体样品注射体积为1uL。载气为氦气,流速恒定为1mL/min。
GC-AED分析使用Agilent GC-7890A,具有JAS AED。GC柱是Agilent DB1(60m×0.25mm i.d.,膜厚1.0μm)。柱温在40℃下保持3min,然后升至320℃(5℃/min),保持10min。注射器的温度保持在350℃,分流比为10:1。液体样品注射体积为1uL。载气为氦气,流速恒定为1mL/min。试剂气体为O2、H2和10%CH4/90%N2用于氧(for oxygen)。
第一组实验在实验室间歇式氢化反应器中进行。
实施例1
将3g来自CarboTech AC GmbH、比表面积为550m2/g的市售活性炭加入到60mL的热解油中,热解油由不可回收的消费后混合聚烯烃废料(以聚乙烯、聚丙烯和聚苯乙烯为主要成分)的热解获得。然后在室温下搅拌该溶液1小时。
实施例2
具有5wt.%Pd的钯-氧化铝催化剂在250℃、30bar的氢气下预活化1小时。然后,加入0.9g预活化的催化剂后将实施例1的溶液(~40mL)加入到高压釜反应器中。加入30bar的氢气,在搅拌下将溶液加热至300℃。持续供应30bar的氢气。
表1:
注意:连续H2进料表示向反应器的恒定H2进料(通向反应器的H2阀门打开)。
随后通过GC-MS和GC-AED对液体进行分析。表2和表3列出了对化学品的氢化。
表2:
表3:
对鉴定出的杂质(N、S、Cl和O)的分析以及与活性炭预接触的效果如下表4所示。
表4:
实施例 | 总N[ppm] | 总S[ppm] | 总Cl[ppm] | 总O[ppm] |
初始 | 912 | 0.7 | 531.3 | 1630.4 |
1 | 877.5 | 0.3 | 400.5 | 1531.2 |
2 | 521.8 | 0.0 | 58.8 | 1190.0 |
在实验室间歇氢化反应器中进行了另一组实验,对诸如催化剂用量、反应时间、反应温度、氢气进料等参数进行了分析。
实施例3-7
具有5wt.%Pd的钯-氧化铝催化剂在250℃、30bar的氢气下预活化1小时。然后,加入预活化催化剂后将实施例1的溶液加入到高压釜反应器中。加入氢气,在搅拌下加热溶液。实施例3至7记录在表5中。
注意:在表5中,不持续的H2进料对应于反应器进行一次氢气填充(通向反应器的H2阀门关闭)。持续的H2进料表示向反应器的恒定H2进料(通向反应器的H2阀门打开)。
实施例3至7的液体随后通过GS-MS和GC-AED进行分析。表6至表8列出了对化学品的氢化。
表6:
表7:
表8:
鉴定出的杂质(N、S、Cl和O)的分析列出如下表9中。
表9:
实施例 | 总N[ppm] | 总S[ppm] | 总Cl[ppm] | 总O[ppm] |
初始 | 912 | 0.7 | 531.3 | 1630.4 |
3 | 1072.0 | 0.4 | 257.6 | 1586.0 |
4 | 1160.4 | 0.0 | 184.7 | 1457.6 |
5 | 756.1 | 0.0 | 122.4 | 1290.6 |
6 | 671.2 | 0.0 | 66.8 | 1116.6 |
7 | 647.4 | 0.0 | 83.2 | 1360.5 |
上表中“初始”是指未经处理的热解油。
Claims (15)
1.用于净化热解塑料废料的方法,所述方法包括以下步骤:
a、提供热解塑料废料,其中,所述热解塑料废料在20℃和1atm下为液体或蜡;
b、将所述热解塑料废料与活性炭接触,产生预处理塑料废料,其中,步骤b)在第一容器中进行;
c、使用氢气和金属基催化剂对所述预处理塑料废料进行氢化,产生氢化塑料废料,其中,步骤c)在第二容器中进行。
2.根据权利要求1所述的方法,其中,所述塑料废料包括含有聚烯烃、聚氯乙烯、聚苯乙烯或其混合物的废料。
3.根据前述权利要求中任一项所述的方法,其中,所述金属基催化剂包含至少一种金属和载体。
4.根据权利要求3所述的方法,其中,所述载体包含由二氧化硅、碳和/或金属氧化物及其混合物组成的列表中选择的化合物。
5.根据权利要求3或4所述的方法,其中,所述载体包含氧化铝。
6.根据前述权利要求3-5中任一项所述的方法,其中,所述金属基催化剂的金属包括从第6组金属和/或第9-11组金属的列表中选择的金属。
7.根据权利要求6所述的方法,其中,所述金属基催化剂的金属包括从第10组金属的列表中选择的金属。
8.根据权利要求7所述的方法,其中,所述金属基催化剂的金属包括钯。
9.根据前述权利要求3-8中任一项所述的方法,其中,所述金属基催化剂以0.1-10wt.%的量包含所述金属。
10.根据前述权利要求中任一项所述的方法,其中,所述金属基催化剂被预活化。
11.根据权利要求10所述的方法,其中,所述金属基催化剂在氢气的存在下被预活化。
12.根据前述权利要求中任一项所述的方法,其中,氢化步骤c)在200-400℃的温度下进行。
13.根据前述权利要求中任一项所述的方法,其中,氢化步骤c)在相对于预处理塑料废料量为0.1-100.0 1/h的重量时空速度(WHSV)下进行。
14.根据前述权利要求中任一项所述的方法,其中,用于对预处理塑料废料进行的氢化步骤c)的氢气以压力为至多100bar的气体提供。
15.根据前述权利要求中任一项所述的方法,其中,步骤b)在相对于热解塑料废料量为0.1-50.0 1/h的重量时空速度(WHSV)下进行。
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- 2021-05-25 WO PCT/EP2021/063832 patent/WO2021239699A1/en unknown
- 2021-05-25 BR BR112022024049A patent/BR112022024049A2/pt unknown
- 2021-05-25 EP EP21728222.7A patent/EP4157968A1/en active Pending
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BR112022024049A2 (pt) | 2022-12-20 |
US20230159836A1 (en) | 2023-05-25 |
EP4157968A1 (en) | 2023-04-05 |
KR20230002990A (ko) | 2023-01-05 |
CA3180070A1 (en) | 2021-12-02 |
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